Flame Retardant Photoimagable Coverlay Compositions and Methods Relating thereto

ABSTRACT

The present invention is directed to phosphorus containing (or “halogen free”) flame retardant photoimagable compositions useful as a coverlay material in a flexible electronic circuitry package. These compositions are generally photosensitive and comprise phosphorus containing acrylates and phosphorus-containing photo-initiators mixed with a polymer binder. The compositions of the present invention typically comprise elemental phosphorus in an amount between, and including, any two of the following numbers 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8 and 6.0 weight percent.

BACKGROUND INFORMATION

1. Field of the Disclosure

The present invention relates generally to flame retardant electroniccircuitry packaging. More specifically, the methods and compositions ofthe present invention are directed to the use of flexible,aqueous-processible, photoimagable coverlay compositions having little,if any, halogen (compared to conventional flame retardant coverlays),due at least in part to the use of a phosphorus based chemistry.

2. Description of Related Art

Photosensitive coverlay compositions can be generally referred to as“solder masks.” These compositions are discussed broadly in U.S. Pat.No. 5,536,620 to Dueber et al. Flame retardant properties (i.e., flameretardancy) can be important in certain applications. Typically,halogenated materials have been used to make these materials flameretardant. However recently, increasing environmental concerns haverequired manufactures to make halogen-free flame retardant coverlaymaterials for flexible printed circuit board markets. Phosphoruscontaining materials have been the focus for these halogen-free flameretardant composition, however phosphorus “bleed” and poor flexibilityhave been two of the many problems identified. A need therefore existsto address such shortcomings.

SUMMARY

The present invention is directed to phosphorus containing flameretardant photoimagable compositions, having comparatively little, ifany, halogen. The compositions of the present invention are generallyuseful as coverlay materials in flexible electronic circuitry packages.In one embodiment, the compositions of the present invention have apolymeric binder comprising: i. photosensitive compounds comprising aphosphorus moiety and an acrylate moiety; and/or ii. aphosphorus-containing photo-initiator. The compositions of the presentinvention typically comprise phosphorus in an amount between, andincluding, any two of the following numbers 2.0, 2.2, 2.4, 2.6, 2.8,3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6,5.8 and 6.0 weight percent.

DETAILED DESCRIPTION

The following discussion is directed to the preferred embodiments of thepresent invention only, and nothing within the following disclosure isintended to limit the overall scope of this invention. The scope of thepresent invention is to be defined solely by the claims, as presented atthe end of this specification.

The present invention is directed to compositions useful as coverlaymaterials for protecting fine line circuitry found on flexiblesubstrates. These compositions contain be photo-active (i.e.,light-active) materials making them useful in photolithographicprocessing. In addition, these materials are regarded as being flameretardant according to the applicable industry standards and do notemploy conventional amounts of environmentally harmful halogenmaterials, i.e., the amount of halogen is equal to or less than 10,000,5000, 1000, 500, 100, 50, 25, 10, 5, 2 or 1 ppm (parts per million)based upon weight.

In one embodiment of the present invention, the coverlay composition isplaced over circuit traces as a sheet and vacuum-pressed, and/orroll-pressed, thereby bonding the coverlay onto the circuit traces.Here, ‘coverlay passageways’ can be formed via any conventional ornon-conventional photo imaging process.

The photo imaging can be accomplished by applying electromagneticradiation through a pattern (commonly called a photo mask), so theradiation exposes only certain pre-defined portions of the coverlay. Theexposed portions will typically have much lower aqueous carbonatesolubility properties than the remaining unexposed portions, due atleast in part to crosslinking, chain extension, and other chemicalreactions in the photo sensitive coverlay.

Thereafter, the coverlay can then be subjected to an aqueous carbonateremoval process. The differential in solubility between the exposed andunexposed portions (due to photo imaging) will generally cause theunexposed portions of the coverlay to swell and dissolve (or otherwisebe removed). As portions of the coverlay are removed, passageways(through the coverlay) can be formed, and then additional curing step isapplied to yield a thermally cross-linked network. Subsequently, thesepassageways are typically filled with metal, via a metal depositionchemistry and process.

Generally speaking, the coverlay materials of the present inventionemploy the use of phosphorus containing monomers (and/or phosphoruscontaining oligomer materials) with a phosphorus containingphoto-initiator. Typically, the phosphorus-containing monomer (oroligomer) is an acrylate. The compositions of the present inventiontypically comprise phosphorus in the total composition an amountbetween, and including, any two of the following numbers 2.0, 2.2, 2.4,2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2,5.4, 5.6, 5.8 and 6.0 weight percent.

The combination of phosphorus-containing monomers (typically acrylates)and phosphorus-containing photo-initiators can create a polymer network,using actinic light radiation and free radical polymerization, wherebythe phosphorus content of the total composition can be maximized (thusmaximizing the physical attributes provided by phosphorus) withoutunduly compromising other physical properties. By polymerizing thecompositions of the present invention in this manner, phosphorus can befixed into a three-dimensional polymer network in order to make both aflame retardant and flexible coverlay material.

As used herein, the term “unsaturated phosphorus-containing monomer” isused to describe any acrylate monomer or acrylate oligomer (or acrylatepolymer formed from either an acrylate monomer or acrylate oligomer orboth) having at least one ethylenical double bond and having at leastone atom of phosphorous. Typically, the compositions of the presentinvention can comprise phosphorus containing acrylates in an amountbetween and including any two of the following numbers 20, 25, 30, 35,40, 45, 50, 55, 60, 65 and 70 weight percent of the total composition.For example, an ester based polymer precursor derived from a phosphatetype compound can be prepared from phosphoric acid, or phosphoric acidderivatives, and alcohol or alcohol based derivatives. In addition,urethane acrylates and epoxy acrylates can be prepared fromhydroxyl-group containing phosphorus derivatives based on phosphoricacid, phosphine oxide or phosphinates.

Some phosphorus-containing monomers include, but are not limited to,commercially available V-3PA® (manufactured by Osaka Organic Chemical),MR-260® (manufactured by Daihachi Chemical), PM-2® and PM-21®(manufactured by Nihon Kayaku), RAYLOK 1721® and RAYLOK 1722®(manufactured by Surface Specialties). The amount of acrylatefunctionality containing within the phosphorus-containing monomer canimpact the flexibility of cured coverlay. In general, lowerconcentrations are generally preferred such as the concentration foundusing RAYLOK®1722 (where the molecular weight is about 1500). Higherconcentrations of acrylate functionality can be used such as monomerslike PM-2® (where the molecular weight is about 166) and V-3PA® (wherethe molecular weight is about 130). However where higher concentrationsof acrylate functionality are used typically other flexible monomers,like urethane acrylate oligomers, are also used so that good flexibilityof the final coverlay is maintained.

As used here, the term “phosphorus containing photo-initiator” isintended to mean a photo-initiator containing the phosphorus atom in itsstructure. In one embodiment, acylphosphine oxide photo-initiator isused as a ‘alpha-cleavage’ photo-initiator creating two free radicalsupon irradiation and initiating free radical polymerization. In anotherembodiment, the phosphorus moiety of the phosphorus-containingphoto-initiator is attached to the end of the photo-initiator compoundto aid in polymerization with other components.

Typically, the compositions of the present invention can comprisephosphorus containing photo-initiator in an amount between and includingany two of the following numbers 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0,10.0, 12.0, 14.0, 16.0 and 18.0 weight percent of the total composition.Examples of useful phosphorus-containing photo-initiators include, butare not limited to, LUCIRIN TPO® and LUCIRIN TPO-L® and IRGACURE 819®.LUCIRIN TPO® and LUCIRIN TPO-L® are monoacylphosphine oxides. IRGACURE819®, and its product family are bisacylphosphine oxides. In general,monoacylphosphine oxides can be useful due to their higher phosphoruscontent compared to bisacylphosphine oxides.

In one embodiment of the present invention, a phosphorous containingphotoinitiator based on acylphosphine oxide can be used to initiate freeradical polymerization with unsaturated double bonds found in aphosphorus containing acrylic monomer (or unsaturated phosphorouscontaining oligomer). The composition formed via this reaction can bedescribed as a three-dimensional polymer network consisting ofphosphorus incorporated into the network. Here, the phosphorus isincorporated into the polymer matrix from two sources, namely theunsaturated phosphorus-containing acrylate component and thephosphorus-containing photo-initiator component.

Introducing phosphorus using both of these components allows one toincrease, to a sufficient level, the amount of phosphorus contained inthe coverlay composition. This allows one to form a coverlay materialthat is flame-retardant (without the use of halogenated materials) whilestill maintaining a variety of other beneficial physical properties suchas good flexibility.

In another embodiment of the present invention, derivatives of phosphineoxides (including phosphinates and phosphates) have been found to beuseful. Typically, these materials can contain chemically reactivehydroxyl end groups that can incorporate with a thermal crosslinkingagent like a blocked isocyanate. Here, phosphorus can be fixed into thepolymer binders of present invention either through physicalentanglement with the other components or by direct connection via achemical bond. In another embodiment, alkaline developable resincontaining chemically reactive carboxylic acid bond sites can also beused. In one instance, unsaturated double bonds positioned on polymerside chains can be useful in aiding polymerization of the binder andphosphorus-containing materials. In another instance, chemicallyreactive hydroxyl groups in the polymer binder can be used to aid inchemically reacting with a thermal crosslinking agent like a blockedisocyanates during thermal curing.

Useful derivatives of phosphine oxides include, but are not limited to,1,4-cyclooctylenephosphonyl-1,4-benzene diol,9-hydroxy-10-(2,5-dihydroxyphenyl)-9-oxo-10-phosphaphenanthorene-10-oxide,n-butyl-bis (3-hydroxypropyl) phosphine oxide, tris(3-hydroxypropyl)phosphine oxide, and2-(9,10-dihydro-9-oxa-10-oxide-10-phosphananthrene-10-yl)methyl succinicacid bis-(2-hydroxyethyl)-ester.

In one embodiment of the present invention, the phosphorus-containingphoto-initiator can be represented by the following formula,

In another embodiment, the phosphorus-containing photo-initiator can berepresented by the following formula,

In one embodiment of the present invention a polymer binder (oroligomers of at least two repeating monomer units) having unsaturateddouble bonds, reactive carboxylic acid groups, or reactive hydroxyl endgroups can be used. In general, reactive groups located on the polymerbinders of the present invention can allow these polymers to react (ornetwork) more completely with a phosphorus-containing monomer/oligomerand phosphorus-containing photo-initiator. Here, thephosphorus-containing monomers of the present invention can beeffectively chemically connected into the polymer network. In general,carboxylic acid functionality can impart ‘alkaline developability’(which can be desirable to many end-users) and hydroxyl end groups canact as an additional reaction site for thermal crosslinking agentsincluding isocyanates.

In one embodiment of the present invention, acrylic co-polymers havingany of these features can be particularly useful. Some of these acrylicco-polymers include, but are not limited to, glycidyl(meth)acrylatederivatives reacted with acid-containing acrylic co-polymer, andmethacryloyl ethyl isocyanate reacted with hydroxyethyl acrylate (HEA)or 2-hydroxyethyl methacrylate (HEMA). (Meth)acrylic acid, and otheracid containing (meth)acrylates (and other copolymerized acid containingmaterials) can also be useful. In another embodiment, modified epoxyresin prepared using a 2-step reaction (a reaction of epoxy resin and(meth)acrylic acid followed by a reaction between the resultant hydroxylgroup and an acid anhydride) can also be a suitable polymer binder.

Photosensitive Compositions:

In many embodiments of the present invention, the compositions furthercomprise additional components. These components can be catalysts,adhesion promoters, other non-halogen flame retardant additives, otherphoto-initiators and the like. These components can be used to renderthe compositions reactive to thermal and/or radiant energy therebymaking the compositions useful in a variety of photoimagable coverlayapplications.

“Photo-active,” which is synonymous with “photosensitive,” describes amaterial that changes its chemical or physical nature, or causes such achange, upon exposure to actinic radiation, in such a way that thechange is formed directly. Examples include an image, or a precursor (alatent image is formed which upon further treatment produces the desiredchange). Photo-active components can include, but are not limited to,photo-initiators, photo-sensitizers, photosolubilizers,photodesensitizer, photoinhibitor, phototackifier, photodetackifier, acomponent that is photodegradable, photochromic, photoreducible,photo-oxidizable, photoadhesive, photoreleaseable, photomagnetic,photodemagnetic, photoconductive, photoinsulative, combinations thereof,and materials that change refractive index upon exposure to actinicradiation. Such photosensitive compositions of this invention include:

(i) a polymerizable monomer, and

(ii) an initiating system activatable by actinic radiation.

“Thermally active” describes a material that changes its chemical orphysical nature (or causes such a change) when its temperature is raisedor when a substance is added or removed. Illustrative of such a photoactive or thermally active component is a material which cyclizes,dimerizes, polymerizes, cross-links, generates a free radical, generatesan ionic species or dissociates upon exposure to actinic radiation orwhen it is heated.

In one embodiment, the phosphorus compounds of the present invention areuseful as components of photosensitive systems and particularly inphotoimaging systems such as those described in “Light-SensitiveSystems: Chemistry and Application of Nonsilver Halide PhotographicProcesses” by J. Kosar, John Wiley & Sons, Inc., 1965 and more recentlyin “Imaging Processes And Materials—Neblette's Eighth Edition,” editedby J. Sturge, V. Walworth and A. Shepp, Van Nostrand Reinhold, 1989. Insuch systems, actinic radiation impinges on a material containing aphotoactive component to induce a physical or chemical change in thatmaterial. A useful image, or latent image, can be processed andproduced. Typically actinic radiation useful for imaging is lightranging from the near ultraviolet through the visible spectral regions,but in some instances may also include infrared, deep-ultraviolet, X-rayand electron beam radiation.

Upon exposure to actinic radiation, the photo active component generallyacts to change the rheological state, the solubility, the surfacecharacteristics, refractive index, the color, the electromagneticcharacteristics and/or other such physical or chemical characteristicsof the photosensitive composition, such as is described in theNeblette's publication identified above.

The photosensitive compositions of this invention can be used in theform of a supported film or layer, although unsupported solid objectsmay also be prepared. The photosensitive composition can generally beapplied to a suitable substrate to form a continuous film or layerthereon which can then be exposed to actinic radiation to form an imagedirectly (or a latent image).

Alternatively, the supported layer may be uniformly exposed to actinicradiation to cure or harden the layer, particularly when thephotosensitive composition is applied either in the form of a continuousor patterned layer, such as, a protective finish, a paint or ink. Anyconventional source of actinic radiation may be used including arc,discharge, and incandescent lamps as well as lasers, X-ray and electronbeam units. The layer may be applied as a solution and dried to a solidlayer wherein any conventional coating or printing process may be used.Alternatively, the layer or film may be applied by laminating asupported solid photosensitive layer to the substrate and thenoptionally removing the support.

In some reversal imaging processes, the treatment step can be used tocomplete the formation of the latent image before or during development.Such systems include photopolymer systems, e.g., as disclosed in U.S.Pat. No. 4,198,242 to Pazos or U.S. Pat. No. 4,477,556 to Dueber et al.(both of which are hereby incorporated into this specification byreference, for teachings therein), containing a photoinhibitor whereinimaging exposure generates inhibitor in the exposed areas of the layerand a subsequent uniform exposure to actinic radiation, or in someinstances uniformly heated, generates a latent image in thecomplimentary areas free of photogenerated inhibitor. Such reversalsystems also include photodesensitizable systems, e.g., as disclosed inRoos U.S. Pat. No. 3,778,270, wherein, in the exposed areas, a componentrequired for image or latent image formation is degraded or desensitizedto an inactive form and the component in the unexposed areas isdeveloped into an image or latent image by subsequent treatment with areagent.

Illustrations of such photosensitive systems are described in Chapter 7,“Polymer Imaging” by A. B. Cohen and P. Walker in Neblette's supra,pages 226-262, in which photocrosslinking, photodimerization,photocyclization, photosolubilization, and both ionic and free radicalphotopolymerization, as well as electrostatic photopolymer imaging andsolid imaging are discussed. In Chapter 8, “Low Amplification ImagingSystems” by R. Dessauer and C. E. Looney, pages 263-278, imaging systemsdiscussed include color forming free radical, diazo, and vesicularsystems, photochromism, phototackification and photodetackification aswell as thermal and photothermal systems.

Photopolymerizable Compositions:

In one embodiment, the coverlay compositions of the present inventioncan be particularly useful as photopolymerizable compositions. In suchsystems, the phosphorus-containing monomer (or oligomer) can bepartially reacted or crosslinked into the polymer network in order toimpart other desirable physical and chemical characteristics to both theexposed and unexposed portions of a photopolymerizable composition. Inone embodiment, exposure to actinic radiation can induce the photoinitiator system to begin a chain-propagated polymerization of themonomeric/oligomeric materials via a step-growth mechanism, or by a freeradical addition polymerization reaction.

While many photopolymerizable mechanisms can be contemplated, thecompositions and processes of the present invention can be described inthe more general context of a free radical initiation and additionpolymerization of monomers having one or more terminal ethylenicallyunsaturated groups. In this context the photo-initiator systems of thepresent invention, when exposed to actinic radiation, can act as asource of free radicals (the free radicals being needed to initiatepolymerization of the monomer component).

In one embodiment of the present invention, acylphosphine oxidephoto-initiator (such as LUCIRIN® TPO, TPO-L, IRGACURE®819, orcombinations of these) can posses the proper UV absorptioncharacteristic while more generally known photo-sensitizers may nottypically absorb necessary portions of the radiation spectra. Thus, theeffect described above can in many cases minimize the amount ofnon-phosphorus initiator that needs to be used in the totalphoto-initiator system (or package). In a broader sense, the term “photoactive” can refer to any or all the essential materials needed forphotopolymerization (i.e., the photo initiating system and the monomer).Photopolymerizable compositions can contain mono- or multi-functionalphosphorus-containing acrylate/methacrylate monomer/oligomer as well asnon-phosphorus acrylate/methacrylate monomer/oligomer if desired.

Additional Polymerizable Monomers:

Other suitable monomers useful as a co-monomer/oligomer in thecompositions of the present invention include, but are not limited tothe following, t-butyl acrylate, 1,5-pentanediol diacrylate,N,N′-diethylaminoethyl acrylate, ethylene glycol diacrylate,1,4-butanediol diacrylate, diethylene glycol diacrylate, hexamethyleneglycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycoldiacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanedioldiacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, polyoxyethylatedtrimethylolpropane triacrylate and trimethacrylate and similar compoundsas disclosed in U.S. Pat. No. 3,380,831, 2,2-di(p-hydroxyphenyl)-propanediacrylate, pentaerythritol tetraacrylate,2,2-di-(p-hydroxyphenyl)-propane dimethacrylate, triethylene glycoldiacrylate, polyoxyethyl-2,2-di-(p-hydroxyphenyl)-propanedimethacrylate, di-(3-methacryloxy-2-hydroxypropyl)ether of bisphenol-A,di-(2-methacryloxyethyl)ether of bisphenol-A,di-(3-acryloxy-2-hydroxypropyl)ether of bisphenol-A,di-(2-acryloxyethyl)ether of bisphenol-A,di-(3-methacryloxy-2-hydroxypropyl)ether of tetrachloro-bisphenol-A,di-(2-methacryloxyethyl)ether of tetrachloro-bisphenol-A,di-(3-methacryloxy-2-hydroxypropyl)ether of tetrabromo-bisphenol-A,di-(2-methacryloxyethyl)ether of tetrabromo-bisphenol-A,di-(3-methacryloxy-2-hydroxypropyl)ether of 1,4-butanediol,di-(3-methacryloxy-2-hydroxypropyl)ether of diphenolic acid, triethyleneglycol dimethacrylate, ethylene glycol dimethacrylate, butylene glycoldimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetrioltrimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate,pentaerythritol trimethacrylate, 1-phenyl ethylene-1,2-dimethacrylate,pentaerythritol tetramethacrylate, trimethylol propane trimethacrylate,1,5-pentanediol dimethacrylate, diallyl fumarate, styrene,1,4-benzenediol dimethacrylate, 1,4-diisopropenyl benzene, and1,3,5-triisopropenyl benzene.

A class of monomers/oligomers is alkylene or a polyalkylene glycoldiacrylates prepared from an alkylene glycol of 2 to 15 carbons or apolyalkylene ether glycol of 1 to 10 ether linkages, and those disclosedin U.S. Pat. No. 2,927,024, e.g., those having a plurality of additionalpolymerizable ethylenic linkages particularly when present as terminallinkages. Preferred are those wherein at least one and preferably mostof such linkages are conjugated with a double bonded carbon, includingcarbon double bonded to carbon and to such hetero atoms as nitrogen,oxygen and sulfur. Also preferred are such materials wherein theethylenically unsaturated groups, especially the vinylidene groups, areconjugated with ester or amide structures.

A particularly preferred class of monomers/oligomers can behexamethylene glycol diacrylate, ethoxlated 1,6-hexanediol diacrylate,acrylated aromatic/aliphatic urethane oligomer, bis-phenol A ethoxylated(10-30 mole) diacrylate/dimethacrylate, polyethoxylateddiacrylate/dimethacrylate, polypropoxylated diacrylate/dimethacrylate,polyester modified Bis-phenol A di-acrylate/di-methacrylate, triethyleneglycol diacrylate, tripropylene glycol diacrylate, pentaerythritoltriacrylate, trimethylolpropane triacrylate, polyoxyethylatedtrimethylolpropane triacrylate,

Additional Suitable Photo-Initiators:

Additional photo-initiators can be used in addition to thephosphorus-containing photo-initiators described above. Thesephoto-initiators can have one or more compounds that directly furnishfree-radicals when activated by actinic radiation. The total amount ofphoto-initiator also may contain a sensitizer that is activated by theactinic radiation, causing the compound to furnish the free-radicals.

Photo-initiator systems of the present invention can contain aphoto-sensitizer that extends spectral response into the nearultraviolet, visible, and near infrared spectral regions. A large numberof free-radical generating compounds, including redox systems such asRose Bengal/2-dibutylaminethanol, may be selected to advantage.Photoreducible dyes and reducing agents such as those disclosed in U.S.Pat. Nos.: 2,850,445; 2,875,047; 3,097,096; 3,074,974; 3,097,097;3,145,104; and 3,579,339; as well as dyes of the phenazine, oxazine, andquinone classes; ketones, quinones; 2,4,5-triphenylimidazolyl dimerswith hydrogen donors, and mixtures thereof as described in U.S. Pat.Nos.; 3,427,161; 3,479,185; 3,549,367; 4,311,783; 4,622,286; and3,784,557 can be used as initiators. Other initiators are dye-boratecomplexes disclosed in U.S. Pat. No. 4,772,541. A useful discussion ofdye sensitized photopolymerization can be found in “Dye SensitizedPhotopolymerization” by D. F. Eaton in Adv. in Photochemistry, Vol. 13,D. H. Volman, G. S. Hammond, and K. Gollinick, eds., Wiley-Interscience,New York, 1986, pp. 427-487. Similarly, the cyclohexadienone compoundsof U.S. Pat. No. 4,341,860 can be useful as initiators.

Reacting or Crosslinking Agents:

When the photopolymerizable composition is to be used as a permanentcoating, such as a solder mask, a chemically or thermally activatedreacting or crosslinking agent may be incorporated to improve hightemperature characteristics, chemical resistance or other mechanical orchemical properties. Suitable reacting or crosslinking agents includethose disclosed in U.S. Pat. No. 4,621,043 to Gervay, and U.S. Pat. No.4,438,189 to Geissler et al., such as melamines, ureas, benzoguanamines,and the like.

Examples of suitable reacting or crosslinking compounds include:N-methylol compounds of organic carboxamides such asN,N′-dimethylolurea, N,N′-dimethyloloxamide, N,N′-dimethylolmalonamide,N,N′-dimethylolsuccinimide, N,N′-dimethylolsebacamide,N,N′,N″-trimethylolcitramide, 1,3-dimethylolimidazolidine-2-one,1,3-dimethylol-4,5-dihydroxyimidazidine-2-one,1,3-dimethylolperhydropyrimidine-2-one, trimethylolmelamine,tetramethylolmelamine, hexamethylolmelamine,1,3-dimethylol-5-methylperhydro-1,3,5-triazine-2-one,1,3-dimethylol-5-allylperhydro-1,3,5-triazine-2-one,1,3-dimethylol-5-butylperhydro-1,3,5-triazine-2-one,1,2-bis-[1,3-dimethylolperhydro-1,3,5-triazine-2-one-5-ylethane,tetramethylolhydrazine dicarboxamide, N,N′-dimethylolterephthalamide,N,NI-dimethylolbenzene-1,3-disulfonamide and tetramethylolglycoluril;and C-methylol compounds of phenols, phenol-ethers and aromatichydrocarbons 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyloanisole,2,6-dimethylol-4-methylphenol, 1,3-dimethylol-4,6-diisopropylbenzene,2,2-bis-(4-hydroxy-3,5-dimethylolphenyl)propane, and3,3′-dimethylol-4,4′-dihydroxydiphenyl sulfone.

Instead of the aforementioned methylol compounds, it is also possible touse, for example, the corresponding methyl, ethyl or butyl ethers, oresters of acetic acid or propionic acid. Suitable examples include:4,4′-bismethoxymethyldiphenyl ether, tris-methoxymethyl-diphenyl ether,tetrakis-methoxymethyl hydrazinedicarboxamide,tetrakis-methoxymethyl-glycoluril,tetrakis-hydroxyethoxymethylglycoluril, bis-acetoxymethyldiphenyl ether,hexamethoxymethyl-melamine. In one embodiment, a preferred crosslinkingagent of this class is hexamethoxymethyl melamine.

Other useful reacting or crosslinking agents are compounds containingtwo or more epoxy groups such as the bis-epoxides disclosed in U.S. Pat.No. 4,485,166 to Herwig et al. Suitable bis-epoxides includebis-glycidal ethers of dihydric alcohols and phenols such as bisphenolA, of polyethylene glycol and polypropylene glycol ethers of bisphenolA, of butane-1,4-diol, hexane-1,6-diol, polyethylene glycol, propyleneglycol or polytetrahydrofurane. Bis-glycidyl ethers of trihydricalcohols, such as glycerol can also be used. Preferred reacting orcrosslinking agents of this class are2,2-bis-(4-glycidoxy-phenyl)-propane and2,2-bis-(4-epoxyethoxy-phenyl)-propane.

Preferred reacting or crosslinking agents of this invention are blockedpolyisocyanates. Upon heating a blocked polyisocyanate, blocking groupssplit off to yield a free reactive polyisocyanate. The free reactingpolyisocynate can be easily reacted with a hydroxyl group, especiallywith a primary hydroxyl group to form a urethane linkage. Usefulpolyisocyanates in the present invention include toluene diisocyanate,isophorone diisocyanate, 1,4-naphthalene diisocyanate, 1,6-hexamethylenediisocyanate, tetramethyl xylene dilsocyanate,bis(4-isocyanatocyclohexyl)methane and the like. Useful blocking groupsare derived from caprolactam; diethyl malonate; alcohols; phenols;oximes, e.g., methyl ethyl ketoxime; and the like.

Adhesion Promoters:

When the photopolymerizable composition is to be attached to a metalsurface, a heterocyclic or mercaptan compound may be added to improveadhesion of the composition to a metal.

Suitable adhesion promoters include heterocyclics such as thosedisclosed in U.S. Pat. No. 3,622,334 to Hurley et al., U.S. Pat. No.3,645,772 to Jones, and U.S. Pat. No. 4,710,262 to Weed. Examples ofuseful adhesion promoters include benzotriazole, 5-chloro-benzotriazole,1-chloro-benzotriazole, 1-carboxy-benzotriazole,1-hydroxy-benzotriazole, 1,2-napthotriazole, benzimidazole,mercaptobenzimidazole, 5-nitro-2-mercaptobenimidazole,5-amino-2-mercyptobenzimidazole, 2-amino-benzimidazole,5-methyl-benzimidazole, 4,5-diphenyl-benzimidazole,2-guanadino-benzimidazole, benzothiazole,2-amino-6-methyl-benzothiazole, 2-mercaptobenzothiazole,2-methyl-benzothiazole, benzoxazole, 2-mercaptobenzoxazole,2-mercaptothiazoline, benzotriazole, 3-amino-1,2,4-triazole,1H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiodiazole-2-thiol,4-mercapto-1H-pyrazolo[3,4-d]pyrimidine,4-hydroxy-pyrazolo[3,4-d]pyrimidene, 5-amino-tetrazole monohydrate,tolutriazole, 1-phenyl-3-mercapototetrazole, 2-amino-thiazole, andthio-benzanilide.

Preferred adhesion promoters for use in photoresists and solder masksinclude 2-amino-5-mercaptothiophene, 5-amino-1,3,4-thiodiazole-2-thiol,benzotriazole, 5-chloro-benzotriazole, 1-chloro-benzotriazole,1-carboxy-benzotriazole, 1-hydroxy-benzotriazole, 2-mercaptobenzoxazole,1H-1,2,4-triazole-3-thiol, and mercaptobenzimidazole.

Polymeric Modifiers

The photopolymerizable composition may (optionally) contain additionalpolymeric binders to modify adhesion, flexibility, hardness, oxygenpermeability, moisture sensitivity and other mechanical or chemicalproperties required during its processing or end use. Such modifiers canbe particularly useful in adjusting room temperature creep viscosity, sothe coverlay compositions of the present invention can be stored in arollstock form, without unwanted creep or deformation.

Suitable polymeric binders which can be used in combination with thebinder of this invention include: polyacrylate and alpha-alkylpolyacrylate esters, e.g., polymethyl methacrylate and polyethylmethacrylate; polyvinyl esters, e.g., polyvinyl acetate, polyvinylacetate/acrylate, polyvinyl acetate/methacrylate and hydrolyzedpolyvinyl acetate; ethylene/vinyl acetate copolymers; polystyrenepolymers and copolymers, e.g., with maleic anhydride and esters;polyvinyl pyrrolidone and copolymers, e.g., poly(vinyl pyrrolidone/vinylacetate) saturated and unsaturated polyurethanes; synthetic rubbers,e.g., butadiene/acrylonitrile, acrylonitrile/butadiene/styrene,methacrylate/acrylonitrile/butadiene/styrene copolymers, andstyrene/butadiene/styrene, styrene/isoprene/styrene block copolymers;high molecular weight polyethylene oxides of polyglycols having averagemolecular weights from about 4,000 to 1,000,000; copolyesters, e.g.,those prepared from the reaction product of a polymethylene glycol ofthe formula HO(CH2)_(n)OH where n is a whole number 2 to 10 inclusive,and

-   -   (1) hexahydroterephthalic, sebacic and terephthalic acids,    -   (2) terephthalic, isophthalic and sebacic acids,    -   (3) terephthalic and sebacic acids,    -   (4) terephthalic and isophthalic acids,    -   (5) mixtures of copolyesters prepared from said glycols    -   (6) terephthalic, isophthalic and sebacic acids    -   (7) terephthalic, isophthalic, sebacic and adipic acid; nylons        or polyamides, e.g., N-methoxymethyl polyhexamethylene        adipamide; cellulose esters, cellulose acetate, cellulose        acetate succinate and cellulose acetate butyrate; cellulose        ethers, e.g., methyl cellulose, ethyl cellulose and benzyl        cellulose; polycarbonates; polyvinyl acetal, e.g., polyvinyl        butyral, polyvinyl formal; polyformaldehydes.

Useful amphoteric polymers include interpolymers derived fromN-alkylacrylamides or methacrylamides, acidic film-forming comonomer andan alkyl or hydroxyalkyl acrylate such as those disclosed in U.S. Pat.No. 4,293,635. For aqueous development the photosensitive layer will beremoved in portions which are not exposed to radiation but will besubstantially unaffected during development by a liquid such as whollyaqueous solutions containing 1% sodium carbonate by weight. A specific,preferred class of polymeric binder modifiers are polyvinyl pyrrolidonepolymers and copolymers thereof, and amphoteric polymers and copolymersthereof.

Plasticizers

The photopolymerizable compositions may also contain a plasticizer tomodify adhesion, flexibility, hardness, solubility, and other mechanicalor chemical properties required during its processing or end use.However, a dedicated plasticizer may not be necessary, particularly ifplasticizer properties are obtained from other ingredients formulatedinto the coverlay for other purposes or functions.

Suitable plasticizers include triethylene glycol, triethylene glycoldiacetate, triethylene glycol dipropionate, triethylene glycoldicaprylate, triethylene glycol dimethyl ether, triethylene glycolbis(2-ethylhexanoate), tetraethylene glycol diheptanoate, poly(ethyleneglycol), poly(ethylene glycol) methyl ether, isopropylnaphthalene,diisopropylnaphthalene, poly(propylene glycol), glyceryl tributyrate,diethyl adipate, diethyl sebacate, dibutyl suberate, dioctyl phthalate,tricresyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate.

Fillers:

The photopolymerizable compositions may also contain suitable organic orinorganic fillers to improve flame retardant, thermal resistance,physical properties and the thixotropic nature of these compositions.For example, Al(OH)₃ and Mg(OH)₂ are well-known inorganic flameretardants. Zinc borate is another class of inorganic flame retardantfillers. Additional fillers useful in the present invention aremicrocrystalline thickeners as disclosed in U.S. Pat. No. 3,754,920,e.g., microcrystalline cellulose, microcrystalline silicas, clays,alumina, bentonite, kalonites, attapultites, and montmorillonites.Another class of fillers includes finely divided powders having aparticle size of 5 nanometers to 50 microns, preferably 5 nanometers to500 nanometers, as disclosed in U.S. Pat. No. 3,891,441, such as siliconoxide, titanium oxide, carbon black, zinc oxide, and other commerciallyavailable pigments.

Melamine polyphosphate, melamine cyanurate, ammonium polyphosphate, andsome of organic phosphorus materials that cannot be dissolved in commonorganic solvent can be regarded as fillers in this invention.

Optional Components:

Other compounds conventionally (or even non-conventionally) can be addedto photosensitive compositions to modify the physical properties of thefilm for a particular use. Such components include: other polymericbinders, fillers, thermal stabilizers, hydrogen donors, thermalcrosslinkers, optical brighteners, ultraviolet radiation materials,adhesion modifiers, coating aids, and release agents. The photopolymerizable compositions may contain other components such as thermalpolymerization inhibitors, dyes and pigments, optical brighteners andthe like to stabilize, color or otherwise enhance the composition.

Thermal polymerization inhibitors that can be used in the photopolymerizable compositions are: p-methoxyphenol, hydroquinone, and alkyland aryl-substituted hydroquinones and quinones, tert-butyl catechol,pyrogallol, copper resinate, naphthylamines, beta-naphthol, cuprouschloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine,nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. Alsouseful for thermal polymerization inhibitors are the nitrosocompositions disclosed in U.S. Pat. No. 4,168,982.

Various dyes and pigments may be added to increase the visibility of theresist image. Any colorant used, however, should preferably betransparent to the actinic radiation used.

Coating Liquids:

The photoimageable, permanent coating may be coated as a liquid onto theprinted circuit substrate using any conventional coating process. Theliquid may be a solution or a dispersion of the permanent coatingcomposition wherein the solvent is removed sufficiently, after coating,to form a tack-free coverlay layer. The additional layer or layers arecoated sequentially and dried. The liquids may be spray coated,roller-coated, spin-coated, screen-coated or printed as disclosed in theCoombs patent discussed above, in the DeForest patent discussed above,in U.S. Pat. No. 4,064,287 to Lipson et al., or in U.S. Pat. No.4,376,815 to Oddi et al. The liquid, typically as a solution, may alsobe curtain coated as disclosed in U.S. Pat. No. 4,230,793 to Losert etal. In the instance where printed circuits are manufactured on acontinuous web of film substrate, permanent coating liquid may be coatedby any conventional (or non-conventional) web coating process.

Photoimageable Coverlay Process:

Photoimageable permanent coatings can be used as a solder mask toprotect printed circuits during subsequent processing, primarily solderoperations, and/or from environmental effects during use. Permanentcoatings also are used as intermediate insulative layers, with orwithout development, in the manufacture of multilayer printed circuits.

In practice, the photoimageable multilayer coating composition,typically between 15 and 50 micrometers (0.6 and 2 mils) thick, isapplied to a printed circuit substrate which typically is a printedcircuit relief pattern on a substrate that is semi-rigid or flexible.The photoimageable coating compositions may be sequentially coated asliquids and dried between layers or may be applied as a pre-coatedsingle layer or multilayer composition on a temporary support. Thecomposition is applied to a printed circuit substrate with vacuumlamination. The applied photopolymerizable composition is then exposedto actinic radiation to harden or insolubilize exposed areas. Anyunexposed areas are then completely removed typically with an alkaline,aqueous sodium or potassium carbonate developer solution whichselectively dissolves, strips, or otherwise disperses the unexposedareas without adversely affecting the integrity or adhesion of theexposed areas. The developed permanent resist image is typically curedat 160° C. for 1 hour. After cure the circuit board has a curedpermanent resist layer covering all areas except unexposed areas thathave been removed by development. Electrical components are thenconnected via the openings in the solder mask via insertion into thethrough-holes or positioned on surface mount areas and soldered in placeto form the packaged electrical component.

Permanent Coating Evaluation:

Printed circuits must withstand a variety of tests that are dependent onthe application of the circuits, which in turn governs the type ofmaterial used as the circuit substrate. A stringent application is forflexible printed circuits which require a fold or bend for a particularspace requirement, such as a camera or video cassette recorder (VCR),and may require the capability of surviving multiple bends, such as in acomputer disc drive. In some applications a flexible circuit is combinedwith a rigid circuit to form a flex-rigid multilayer printed circuit.The end use tests for flexible circuits focus on adhesion and thecapability to withstand a single fold or multiple bends. The process andseveral tests that are used to support the examples in this applicationare described below.

A pre-formed, dry-film, photopolymerizable coating is applied, afterremoval of a removable cover sheet, e.g., polyethylene or polypropyleneused to protect the permanent coating element during storage, to thepre-cleaned copper printed circuit surface of the substrate with a SMVLvacuum laminator. Although the laminate is typically exposed to actinicradiation through the temporary support film, in some instances, thetemporary support may be removed before imaging to improve resolutionand other such properties.

Typically, when a dry film is laminated without a liquid assist to aprinted circuit substrate having a low circuit relief, measures must betaken to eliminate entrapped air, e.g., from around circuit lines.Entrapped air is eliminated by the vacuum lamination process describedin U.S. Pat. No. 4,127,436 to Fiel, or may be eliminated by the groovedroll lamination process described in U.S. Pat. No. 4,071,367 to Collieret al. A Solder Mask Vacuum Laminator (SMVL) is useful in eliminatingentrapped air, but this laminator is limited to atmospheric pressurelamination force after the evacuation cycle. If higher pressure isneeded, the SMVL lamination can be followed by a hot press lamination,or alternatively a vacuum press can be used for the lamination.

Flammability (UL94 TEST):

Specimens were tested in accordance with the UL 94 Thin MaterialVertical Burning Test for classing resist coating materials as 94VTM-0,94VTM-1 or 94VTM-2. The 94VTM-0 classification is the best rating,indicating significantly reduced flammability.

EXAMPLES

The advantages of the present invention are illustrated in the followingexamples. These examples are not intended to limit the scope of thisinvention. The compositions below are described in weight % for eachingredient used.

The following glossary contains a list of names and abbreviations foreach ingredient used:

LUCIRIN TPO ® Diphenyl 2,4,6-trimethyl benzylphosphine oxide from BASFRAYLOK 1722 ® Phosphorus containing Polyester acrylate Oligomer, Mw =3000, Functionality = 2, P- content = 5% from Surface Specialty Chem.Viscoat 3PA ® Tris Acryloyloxy ethyl phosphate from Osaka Organic Chem.EBECRYL 9119 ® 75% by weight solids of urethane di-acrylate from SurfaceSpecialty Chem. DESMODU Hexamethylene diisocyanate BL3175 ® basedpolyisocyanate blocked with methyl ethyl ketoxime and dissolved at 75%solids in ethyl acetate 5-ATT 5-amino-1,3,4-thiadiazole-2-thiol fromAldrich Chemical Co. 3-MT 3-mercapto-1H,2,4-triazole from EspritChemical Co., Rockland, MA CBT Carboxy Benzotriazole BASONYL ® BlueGreen dye from Crompton & Green Knowles Corp., Reading, PA PO-4500n-Butyl-bis (3-hydroxypropyl) Phosphine Oxide from Nihon Kagaku ADK STABFP- Oligomeric Phosphate from 700 ® ADEKA ZFR-1481 ® Bis-phenol F Epoxymodified resin from Nihon Kayaku Acrylic copolymer MAA: 18%, Tg = 30 C.,Mw = 80000 Reactive acrylic MAA: 18%, HEMA: 5%, Reactive copolymer 1acrylate through urethane linkage: 7%, Tg = 30 C., Mw = 80000 Reactiveacrylic MAA: 18%, HEMA: 5%, Reactive copolymer 2 acrylate through epoxylinkage: 7%, Tg = 30 C., Mw = 80,000 BF013S ® Al(OH)3 from NihonKeiKinzoku

Example 1

Each coating solution was coated on 19 um Teijin G2 to have 50 um driedthickness. Coatings were vacuum laminated to a chemically cleanedPYRALUX TM® with a solder mask vacuum laminator at 50° C. Time to clear(TTC) in 1% aqueous sodium carbonate at 40° C. was determined. Theoptimum exposure that is required to obtain 7 steps in SST21 of polymerimage after development using a SST21 wedge photo mask was determined.This optimum exposure was used for the EXAMPLES 1-3. Samples wereexposed, developed at 2 times the time to clear unexposed material, andthe developed samples were air dried and cured at 160° C. for one hour.The processed samples were tested with immersion in 10% sulfuric acid at30° C. for 20 min.

Ingredient % by Weight Reactive acrylic copolymer 1 31.00 RAYLOK 1722 ®47.00 EBECRYL 9119 ® 2.00 PO-4500 6.00 DESMODUR BL3175 ® 6.83 LUCIRINTPO ® 7.00 Sevron Blue 0.04 5-ATT 0.13

This sample passed UL94VTM-0 flame retardancy testing on 25 um KAPTON®E.

Example 2

This EXAMPLE was prepared in accordance with the procedure of EXAMPLE 1.The ingredients used were changed as follows:

Ingredient % by Weight Reactive acrylic copolymer 1 21.00 ZFR1481 ®10.00 RAYLOK 1722 ® 47.00 EBECRYL 9119 ® 2.00 PO-4500 6.00 DESMODURBL3175 ® 6.83 LUCIRIN TPO ® 7.00 Sevron Blue 0.04 5-ATT 0.13This sample passed UL94VTM-0 flame retardancy testing on 25 um KAPTON®E.

Example 3

This EXAMPLE was prepared in accordance with the procedure of EXAMPLE 1.The ingredients used were changed as follows:

Ingredient % by Weight Reactive acrylic copolymer 2 31.00 RAYLOK 1722 ®44.00 Viscoat 3PA 5.00 EBECRYL 9119 ® 2.00 PO-4500 4.00 DESMODURBL3175 ® 6.83 LUCIRIN TPO ® 7.00 Sevron Blue 0.04 3-MT 0.08 CBT 0.05This samples passed UL94VTM-0 flame retardancy testing on 25 um KAPTON®E.

Example 4

This EXAMPLE was prepared in accordance with the procedure of EXAMPLE 1.The ingredients used were changed:

Ingredient % by Weight Reactive acrylic copolymer 1 28.00 RAYLOK 1722 ®48.00 EBECRYL 9119 ® 2.00 DESMODUR BL3175 ® 4.88 LUCIRIN TPO ® 6.00Sevron Blue 0.03 5-ATT 0.09 BF013S 11.00This sample passed UL94VTM-0 flame retardancy testing on 25 um KAPTON®E.

Comparative Example 1

This COMPARATIVE EXAMPLE indicates the need for reactive phosphoruscompound such as a phosphorus containing acrylate oligomer to providegood photo-properties as well as cured properties such as acidresistance. Non-reactive oligomeric phosphate (ADKA STAB FP-700) wasadded to the composition at the expense of a reactive phosphorusacrylate oligomer (RAYLOK® 1722) with same level of total Phosphoruscontent.

Ingredient % by Weight Reactive acrylic copolymer 1 31.00 RAYLOK 1722 ®38.00 EBECRYL 9119 ® 2.00 ADKA STAB FP-700 15.00 DESMODUR BL3175 ® 6.83LUCIRIN TPO ® 7.00 Sevron Blue 0.04 5-ATT 0.13While the sample did pass flame retardancy testing, too muchnon-photo-reactive phosphorus component cause the sample to have poorphoto-performances and poor acid resistance.

Comparative Example 2

This COMPARATIVE EXAMPLE indicates the need for Blocked Isocyanate(DESMODUR BL3175®) to connect hydroxyl group containing Phosphoruscompound (PO-4500) during thermal curing to have better curedproperties.

Ingredient % by Weight Reactive acrylic copolymer 1 31.00 RAYLOK 1722 ®50.00 EBECRYL 9119 ® 5.83 PO-4500 6.00 LUCIRIN TPO ® 7.00 Sevron Blue0.04 5-ATT 0.13While this sample passed flame retardancy testing and had goodPhoto-properties, the sample was not functional due to poor acidresistance.

Comparative Example 3

This COMPARATIVE EXAMPLE indicates the need for the reactive binder tohave better overall chemical resist properties.

Ingredient % by Weight Acrylic copolymer 31.00 RAYLOK 1722 ® 47.00EBECRYL 9119 ® 2.00 PO-4500 6.00 DESMODUR BL3175 ® 6.83 LUCIRIN TPO ®7.00 Sevron Blue 0.04 5-ATT 0.13While this sample passed flame retardancy testing, had suitablephoto-properties and sufficient acid resistance, all three of theseproperties were inferior compared to samples employing a reactiveacrylic co-polymer.

Comparative Example 4

This COMPARATIVE EXAMPLE indicates the need for a certain level ofphosphorus content is generally required to achieve a VTM-0 class flameretardant level.

Ingredient % by Weight Reactive acrylic copolymer 1 31.00 RAYLOK 1722 ®27.00 EBECRYL 9119 ® 22.00 PO-4500 6.00 DESMODUR BL3175 ® 6.83 LUCIRINTPO ® 7.00 Sevron Blue 0.04 5-ATT 0.13While this sample passed a bend and crease test, had sufficient acidresistance and sufficient photo-properties, the sample was not flameretardant.

1. A photosensitive circuit coverlay composition comprising a phosphoruscontaining monomer, a phosphorus containing photo-initiator, and apolymer binder, wherein the total composition has a phosphorus contentin an amount between, and including, any two of the following numbers2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6,4.8, 5.0, 5.2, 5.4, 5.6, 5.8 and 6.0 weight percent.
 2. A composition inaccordance with claim 1 wherein the polymer binder is an acrylic, epoxy,or epoxy modified acrylic polymer.
 3. A composition in accordance withclaim 1 wherein the phosphorus containing monomer is an acrylate that,under radical polymerization, forms a three-dimensional polymer network.4. A composition in accordance with claim 1 wherein the polymer bindercontains an unsaturated bond, carboxylic acid group, acid group orhydroxyl group and wherein the polymer binder is capable of chemicallyreacting with the phosphorus containing monomer andphosphorus-containing photo-initiator.
 5. A composition in accordancewith claim 1 wherein the phosphorus containing monomer, prior to beingchemically reacted with the composition, is an oligomer.
 6. Acomposition in accordance with claim 1 wherein the phosphorus containingmonomer is a mono-functional or multi-functional methacrylate oracrylate derivative.
 7. A composition in accordance with claim 1 whereinthe phosphorus containing monomer contains an unsaturated bond and iscapable of chemical crosslinking.
 8. A composition in accordance withclaim 1 wherein the phosphorus containing monomer is present in anamount between and including any two of the following numbers 20, 25,30, 35, 40, 45, 50, 55, 60, 65 and 70 weight percent of the totalcomposition.
 9. A composition in accordance with claim 1 wherein thephosphorus containing monomer is present in an amount between andincluding any two of the following numbers 30, 35, 40, 45, 50, 55 and 60weight percent of the total composition.
 10. A composition in accordancewith claim 1 wherein the phosphorus containing photo-initiator is aphosphine oxide or acrylphosphine oxide derivative.
 11. A composition inaccordance with claim 1 wherein the phosphorus containingphoto-initiator has the chemical structure,


12. A composition in accordance with claim 1 wherein the phosphoruscontaining photo-initiator has the chemical structure,


13. A composition in accordance with claim 1 wherein the phosphoruscontaining photo-initiator is present in an amount between and includingany two of the following numbers 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0,10.0, 12.0, 14.0, 16.0 and 18.0 weight percent of the total composition.14. A composition in accordance with claim 1 wherein the phosphoruscontaining photo-initiator is present in an amount between and includingany two of the following numbers 4.0, 5.0, 6.0, 7.0 and 8.0 weightpercent of the total composition.
 15. A composition in accordance withclaim 1 further comprising a thermal crosslinking agent.
 16. Acomposition in accordance with claim 1 further comprising a thermalcrosslinking agent wherein the thermal crosslinking agent is a blockedisocyanate or blocked polyisocyanate.
 17. A composition in accordancewith claim 1 further comprising a thermal crosslinking agent wherein thethermal crosslinking agent is a blocked polyisocyanate that upon heatingforms a polyisocyanate selected from the group consisting of toluenediisocyanate, isophorone diisocyanate, 1,4-naphthalene diisocyanate,1,6-hexamethylene diisocyanate, tetramethyl xylene diisocyanate, bis(4-isocyanatocyclohexyl)methane.
 18. A composition in accordance withclaim 1 further comprising a phosphorus containing material, the solublephosphorus containing material further comprising a hydroxyl group. 19.A composition in accordance with claim 18 wherein the phosphoruscontaining material, under thermal reaction or crosslinking, canpolymerize with the phosphorus containing acrylate and polymer binder.20. A composition in accordance with claim 1 further comprising a fillerselected from the group consisting of aluminum hydroxide, magnesiumhydroxide, zinc borate, micro crystalline cellulose, micro crystallinesilicas, clays, alumina, bentonite, kalonites, attapultites,montmorillonites, silicon oxide, titanium oxide, carbon black, zincoxide, melamine polyphosphate, melamine cyanurate, and ammoniumpolyphosphate.
 21. A composition in accordance with claim 20 wherein thefiller has a particle size from 5 nanometers to 10,000 nanometers.
 22. Acomposition in accordance with claim 1 further comprising a photo-activecomponent.
 23. A composition in accordance with claim 1 furthercomprising a photo-active component wherein the photo active componentis selected from the group consisting of photo-initiators,photo-sensitizers, photosolubilizers, photodesensitizer, photoinhibitor,phototackifier, photodetackifier, a component that is photodegradable,photochromic, photoreducible, photo-oxidizable, photoadhesive,photoreleaseable, photomagnetic, photodemagnetic, photoconductive,photoinsulative, combinations thereof, and materials that changerefractive index upon exposure to actinic radiation.
 24. A compositionin accordance with claim 1 further comprising an adhesion promoter. 25.A composition in accordance with claim 1 further comprising an adhesionpromoter selected from the group consisting of2-amino-5-mercaptothiophene, 5-amino-1,3,4-thiodiazole-2-thiol,benzotriazole, 5-chloro-benzotriazole, 1-chloro-benzotriazole,1-carboxy-benzotriazole, 1-hydroxy-benzotriazole, 2-mercaptobenzoxazole,1H-1,2,4-triazole-3-thiol and mercaptobenzimidazole.
 26. A compositionin accordance with claim 1 wherein the composition is flame retardantaccording to UL 94 Thin Material Vertical Burning Test 94VTM-0, UL 94Thin Material Vertical Burning Test 94VTM-1 or UL 94 Thin MaterialVertical Burning Test 94VTM-2.